Electrochemical textile-washing process

ABSTRACT

The present invention relates to a washing machine comprising an electrochemical cell, to a process for electrochemical cleaning of fibers, to laundry detergents for electrochemical cleaning of fibers and to the fibers thus cleaned.

The present invention relates to a washing machine comprising anelectrochemical cell, to a process for electrochemical cleaning offibers, to laundry detergents for electrochemical cleaning of fibers andto the fibers thus cleaned.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows a schematic presentation of the experiment apparatus usedin the examples.

There has been a steadily growing awareness in recent years on the partof the population as to human influence on the environment. Wasteavoidance, reduction and recycling are prominent concerns and arebecoming ever more important. A large proportion of emissions in theprivate sphere is associated with textile cleaning and care, for whichcomplex laundry detergent mixtures are used. Since some ingredients ofthese laundry detergents can have adverse consequences for theenvironment in the long term, the demand for less environmentallyhazardous laundry detergents is increasing. Yet reducing the ingredientsshall not lead to a reduced washing performance. One solution resides inspecific laundry detergents for certain colors or fibers, but leads toan increased number of laundry detergents in households and therefore isnot very consumer-friendly.

Alternatively, performance of the washing machines can be increased.

Especially the bleachingly active compounds represent a challenge.Current laundry detergents include bleach catalysts or bleach precursorsand a peroxide source, ensuring that the bleach is only activated duringthe wash.

One challenge in formulating a laundry detergent is to protect thesensitive ingredients of the laundry detergent (examples being enzymesand perfumes) from the bleach components.

One possible way to do this is to protect the sensitive ingredients fromthe influence of the bleach by encapsulation. This is particularlydifficult to do in the case of liquid laundry detergents, where areaction medium is already present in the formulation in the form ofwater. Separating bleach components and sensitive substances is hereoften only accomplished with the aid of stock reservoir containerscomprising sophisticatedly engineered and not very user-friendlymulticompartment systems. It further needs to be ensured that the bleachis only formed during the wash and not already beforehand, sincebleachingly active substances, such as hydrogen peroxide for example,are unstable under the alkaline conditions typically present,decomposing with gas evolution. Furthermore, many bleach components usedin pulverulent laundry detergents are not sufficiently soluble in liquidlaundry detergents.

One possible way to overcome the limitations described is the in situgeneration of bleachingly active substances in the washing machine. Itis known to electrolytically generate hydrogen peroxide (U.S. Pat. No.6,387,238) and react the hydrogen peroxide with TAED(tetraacetylethylenediamine) to form peracetic acid, known to be ableachingly active compound. US 2002/0,166,177 describes a washingmachine that includes a peroxide generator. EP 1 739 207 claims anelectrolysis unit for in situ generation of peroxide and its use in thefield of textile bleaching. The use of diamond electrodes in dividedcells in conjunction with textile washing is described in JP 2003 211104. The diamond electrodes here are used for the electrochemicaltreatment of the wash water at the end of the wash cycle in the mannerof a wastewater treatment (TOC degradation). In a further aspect,electrolysis is used to form acidic (anolyte) and basic (catholyte)water in order to achieve a superior washing result through sequentialand repeated use of these washing solutions.

However, all the systems are based on a divided electrolytic cell. Adivided electrolytic cell, in addition to a membrane, also requiresadditional containers and pumps in order that the various circuits(anolyte and catholyte) may be operated separately from each other. Thefluxes of material through permeation and electro-osmosis, i.e., throughtransportation of solvent molecules dragged as solvate shell and througha friction effect with the ions through the membrane, have to beappropriately balanced out. The membrane can erode in places where theflow rate is high, and can even be destroyed through “hot spots” whenlocally increased current densities occur. Direct contact of the(flexible) membranes with the electrodes, more particularly the anode,is harmful in the long term, and has to be prevented through technicalmeasures. After installation, the membranes must not be allowed tobecome dry again, since cracks can form inter alia. When sparinglysoluble salts are present in the electrolyte (wash water, wash liquor),the free acids or bases may in certain circumstances crystallize out inthe membrane and thus lead to holes and cracks. Owing to the increasingcomplexity of the system, therefore, it is not just the capital costwhich rises for the end-user, but also the cost of maintenance as wellas the energy consumption due to the additional pumps, structuralcomponents and control units. Technical realization of the frequentlyused gas-diffusion electrodes in the private sphere and the frequentlyvery limited operating life of the membranes (risk of hair cracks, lossof permselectivity) inhibit wide dissemination of the systems. Inaddition, the frequently used gas-diffusion electrode consumes oxygenfor generating hydrogen peroxide. Oxygen, however, has only a limitedsolubility in water (specifically at elevated temperature) and has to bepermanently replenished by introduction of air. Surfactant-containingwashing solutions tend to foam, which is further amplified by additionalblowing in of air and can damage the machine.

The use of diamond electrodes in the context of bleach activation hashitherto not been described. Boron-doped diamond electrodes havehitherto been customarily used in wastewater treatment (TOCdegradation), where the aggressive free OH radicals formed at thiselectrode attack and oxidize organic material as far as CO₂. Therefore,appreciable color and fiber damage was to be expected to occur on use intextile-washing machines.

In principle, electrochemical processes are used in a series ofapplications. In the most frequent applications, individual chemicalsare specifically converted into others. Bond cleavages, dimerizations,couplings and so on can be carried out electrochemically, for example.

Electrochemical processes have hitherto not been commercially used inthe field of textile washing. Reasons include that not all necessaryequipment parameters have been researched; heavy-metal electrodes havehitherto been used, always leading to an input of heavy metal into thewash liquor; and that to date there are no laundry-detergentformulations specifically developed for wash processes of this type.

It is an object of the present invention to provide a system forcleaning fibers—and more particularly textiles—which satisfies thetechnical prerequisites as well as the chemical ones.

We have found that this object is achieved, surprisingly, by the washingmachine according to claims 1 to 4, the process according to claims 5 to9, the laundry detergent according to claim 10 and also the fibersaccording to claim 11, since it was found that, surprisingly,boron-doped diamond electrodes can be used for textile bleaching eventhough these electrodes, typically used in wastewater treatment (TOCdegradation), were expected to give rise to appreciable color and fiberdamage, required no more than a pre-electrolysis of the water (prior tothe addition of laundry detergent, bleach activator and textile fabric)for bleach activation, thereby appreciably reducing the energyrequirements (10 min pre-electrolysis compared with 30 min-60 minsustained electrolysis during the washing operation), and what is more,sensitive constituents of the laundry detergent and the clothes do nothave to be unnecessarily exposed to the electrodes/free OH radicals,

an integration of an electrolytic cell in the external supply of wateris possible, the electrochemical activation of bleach is also compatiblewith liquid laundry detergents,it is possible to use an undivided cell, which is very simple in itsconstruction and low maintenance and therefore very advantageous overdivided cells, and nor are any additional containers, pumps, membranes,etc needed, good bleaching results can be obtained even at low washingtemperatures (<40° C.), and

the use of the electrode in the washing machine has hygienic advantages.

The present invention accordingly provides a washing machine comprisingan electrode and a closed-loop control unit, wherein a current strengthin the range from 0.02 to 30 A can be applied to the electrode duringthe washing operation.

Preference is given to a washing machine where the current strengthwhich can be applied is in the range from 0.1 to 16 A and morepreferably from 0.3 to 10 A.

And preference is given to a washing machine where the current strengthis applied during the filling and/or washing operation.

The current strength can vary over time. Preferred embodiments accordingto the present invention have a constant current strength or a variablecourse for the current strength.

The type of washing machine comprises all types of washing machines,i.e., not only domestic washing machines but also washing machines forindustrial fiber and more particularly textile cleaning. Washingmachines have been extensively described, for example in EP 2 098 627and EP 2 098 628.

The electrode materials, more particularly anode materials, used in theelectrochemical cell are preferably materials with which a high oxygenovervoltage can be achieved, examples being noble metals such asplatinum or metal oxides such as ruthenium oxide, chromium oxide or leadoxide or mixed oxides of the type RuO_(x)TiO_(x) or conventionaldimensionally stable anodes (DSAs) or diamond electrodes.

The electrode is preferably selected from the group consisting ofgraphite electrode, diamond electrode, steel electrode and platinumelectrode.

Diamond electrodes are preferred. They are formed by applying one ormore layers of diamond to a carrier material. Useful carrier materialsinclude niobium, silicon, tungsten, titanium, silicon carbide, tantalum,graphite or ceramic carriers such as titanium suboxide. However, theprocess or method of the present invention preferably utilizes a carriercomposed of niobium, titanium or silicon, and a carrier composed ofniobium is very particularly preferred when a diamond electrode is used.

The anode is preferably a diamond electrode, in which case the diamondelectrode can also additionally be doped with further metals. Boron andnitrogen are preferred for use as doping metals. The process or methodof the present invention is very particularly preferred using aboron-doped diamond (BDD) electrode as anode.

The electrolysis can be carried out using any conventional electrolyticcell comprising the electrodes mentioned—such as divided or undividedcontinuous flow cells, capillary cells or stacked plate cells. Anundivided continuous flow cell is particularly preferred. A bipolararrangement of two or more electrodes is advantageous for achievingoptimum space-time yields.

It was further found, then, that diamond electrodes behave similarly toheavy-metal electrodes under the conditions of fiber and moreparticularly textile washing.

The process or method of the present invention therefore has theadvantage that no metal ions pass into the electrolyte (i.e., the washliquor) and hence the environment, since no heavy-metal ions can form inthe corrosion of the diamond layer of the BDD electrode.

Diamond electrodes obtained by chemical vapor deposition (CVD) can beused. Such electrodes are commercially available, for example from:Condias, Itzehoe (Germany) and/or Adamant Technologies,La-Chaux-de-Fonds (Switzerland).

Less costly diamond electrodes produced by the high-temperaturehigh-pressure (HTHP) process (industrial diamond powder is mechanicallyincorporated in the surface of a carrier metal) are likewise suitable.

HTHP-BDD electrodes are commercially available from pro aqua, Niklasdorf(Austria), and their properties are described by A Cieciwa, R. Wüthrichand Ch. Comninellis in Electrochem. Commun. 8 (2006) 375-382.

With regard to electrode type, therefore, a washing machine where theelectrode is a diamond electrode is preferred.

Useful cathode materials, unless electrode polarity is to beinterchanged, include for example iron, steel, stainless steel ornickel, otherwise also precious metals such as platinum, and alsodiamond electrodes. Preference, however, is given to using boron-dopeddiamond electrodes as cathode.

The process or method of the present invention is preferably carried outusing a diamond electrode as cathode. This diamond electrode comprises alayer of diamond applied to a carrier material, the carrier materialbeing selected from the group consisting of niobium, silicon, tungsten,titanium, silicon carbide, tantalum, graphite or ceramic carriers suchas titanium suboxide. The carrier material is more preferably niobium orsilicon. The diamond layer on the carrier can additionally be doped withfurther elements. Preference is given to boron- or nitrogen-dopeddiamond electrodes. Boron-doped diamond electrodes are particularlypreferred.

Very particular preference is given to the combination of boron-dopeddiamond electrode as anode with steel as cathode, in which case moreparticularly the washing-machine casing of steel acts as cathode. Thesteel used is more particularly stainless steel.

In another preferred embodiment, the washing machine comprises twodiamond electrodes, connected as anode and cathode.

When the anode(s) and cathode(s) are diamond electrodes, theelectrolysis can also be carried out in intervals and, optionally, thepolarity of the electrodes interchanged (short-term electrolysis,washing operation, short-term electrolysis, washing operation, etc). Oneadvantage of this intermittent operation is that sensitive constituentsof the laundry detergent would be only briefly exposed to possibledegradation at the electrodes (primarily through free OH radicals).

The process or method of the present invention is advantageous when thepoling of the diamond electrodes is interchanged in the range from 0.1to 200 min or from wash to wash to avoid electrode fouling.

The individual electrodes are of a certain size which affects theeffect. Preference is given to a washing machine wherein the individualelectrode has an effective surface area in the range from 0.5 to 1000cm², preferably in the range from 1 to 500 cm² and more preferably inthe range from 2 to 100 cm². The electrode size here is based on thesurface area of the individual electrode which during the electrolysisis connected as anode and faces the cathode. When an anode is positionedbetween two cathodes, the electrode size of the anode is the sum totalof the front and reverse surfaces. The effective electrode area of theindividual electrode is the electrode area of the anode which during theelectrolysis comes into contact with the electrolyte and faces thecathode(s).

When two electrodes are connected such that they can functionalternatingly as an anode or as cathode, the values resulting for theoverall electrode area are accordingly twice as large.

The effective areas of the anode(s) and cathode(s) are preferably ofequal size, which is particularly preferable when the anode(s) and thecathode(s) alike are diamond electrodes. The electrodes are arranged acertain distance apart. A distance of 0.1-20 mm is preferred, a distanceof 1-10 mm is preferable and of 2-5 mm is more preferable.

An electrolytic cell according to the present invention comprises a pairof electrodes which are preferably not separated from each other by amembrane. A bipolar arrangement of two or more electrodes isadvantageous to optimize the space-time yields.

Inside the washing machine, the cell is installed in the flooded regionof the washing tub, preferably outside the washing drum. However, thecell can also be mounted in the supply line inside or outside thewashing machine. The cell can be a fixedly installed constituent of thewashing machine or a separate component (for example in the fresh-watersupply line between the stop cock and the washing machine, or as ane-bleach ball with its own energy supply in the drum). Such a kit ofparts comprising a washing machine and an electrolytic cell connectableupstream at the water inlet constitutes a further part of the subjectmatter of the present invention. A further embodiment according to thepresent invention consists in integrating the electrolytic cell in anadditional water circuit within the machine.

An e-bleach ball, comprising a power supply independent of theelectricity grid, a diamond anode and a cathode, which are arranged suchthat the electrodes are able to come into contact with the electrolytewhen the e-bleach ball is in the washing drum of a washing machineduring the washing operation, forms a further part of the subject matterof the present invention.

The present invention further provides a process for cleaning fibers,which comprises generating free OH radicals and H₂O₂ in aqueous solutionby applying a current strength in the range from 0.02 to 30 A to anelectrode.

The process or method of the present invention utilizes an electrolyteselected from the group consisting of water, methanol and ethanol. Wateris particularly preferred.

In the process or method of the present invention, the pH is in therange from 2 to 13, preferably in the range from 3 to 12 and morepreferably in the range from 6 to 11.

The temperature for the process or method of the present invention is inthe range from 10 to 95° C., preferably in the range from 15 to 90° C.,more preferably in the range from 20 to 60° C. and even more preferablyin the range from 25 to 40° C., such as 30° C. for example.

Further general parameters of such a process or method are discerniblefrom EP 2 088 231 for example.

Preference is further given to a process wherein the electrode is adiamond electrode having an effective surface area in the range from 0.5to 1000 cm², preferably in the range from 1 to 500 cm² and morepreferably in the range from 2 to 100 cm².

A process wherein at least one compound selected from the groupconsisting of builder, surfactant and enzyme is used for cleaning aswell as the free OH radicals (or its descendent products such ashydrogen peroxide and ozone), constitutes a preferred version.

These compounds are preferably included in the laundry detergent of thepresent invention. Nonexhaustive examples of builders, surfactants andenzymes are recited there.

Preference is further given to a process carried out at a temperature upto 60° C., preferably up to 40° C. and more preferably up to 30° C.

A process as described above that has an at least 20% degree of soilremoval for bleachable stains (tea for example) forms a further part ofthe subject matter of the present invention.

The degree of soil removal is determined as follows:

A white cotton test fabric is initially stained and is subjected to areflectance measurement at 460 nm before and after performance of theprocess or method, i.e., before and after washing. Soil removal isdetermined from the reflectance values R before and after performance ofthe process or method and the reflectance value of a white referencecotton fabric as per the following formula, in %:

${{Degree}\mspace{14mu} {of}\mspace{14mu} {soil}\mspace{14mu} {{removal}\lbrack\%\rbrack}} = {\frac{{R\left( {{after}\mspace{14mu} {wash}} \right)} - {R\left( {{before}\mspace{14mu} {wash}} \right)}}{{R\left( {{white}\mspace{14mu} {cotton}} \right)} - {R\left( {{before}\mspace{14mu} {wash}} \right)}} \times 100}$

All washes are carried out twice and averaged.

The reflectance measurements are carried out using a Gretag MacbethSpectrolino spectrophotometer under the following conditions: observerangle 10°, illuminant D65, UV filter.

A laundry detergent, more particularly a fully built laundry detergent,comprising bleach activator(s) and/or bleach catalyst(s) and less than1% by mass of hydrogen peroxide or of hydrogen peroxide releasercompounds, is a further part of the present invention.

Similarly, a liquid laundry detergent comprising bleach activator(s)and/or bleach catalyst(s) is part of the subject matter of the presentinvention. The liquid laundry detergent contains the bleach activator inan amount of at least 0.01% to 10% by mass, preferably from 0.1% to 5%by mass and more preferably from 0.5% to 3% by mass. The bleachactivator is preferably selected from the hereinbelow recited suitablebleach activators. The bleach activator TAED is particularly preferred.

A prespotter comprising bleach activator(s) and/or bleach catalyst(s)forms a further part of the subject matter of the present invention. Theprespotter comprises the bleach activator in an amount of at least 0.01%to 50% by mass, preferably from 0.1% to 30% by mass and more preferablyfrom 0.5% to 10% by mass. The bleach activator is preferably selectedfrom the hereinbelow recited suitable bleach activators. The bleachactivator TAED is particularly preferred.

Useful bleach activators include:

-   -   polyacylated sugars, e.g., pentaacetyl glucose;    -   acyloxybenzenesulfonic acids and their alkali and alkaline earth        metal salts, e.g., sodium p-isononanoyloxybenzenesulfonate or        sodium p-benzoyloxybenzenesulfonate;    -   acyloxybenzoic acids and their alkali and alkaline earth metal        salts, e.g., sodium p-nonanoyloxybenzoic acid or sodium        p-decanoyloxybenzoic acid;    -   N,N-diacylated and N,N,N′,N′-tetraacylated amines, e.g.,        N,N,N′,N′-tetraacetyl-methylenediamine and -ethylenediamine        (TAED), N,N-diacetylaniline, N,N-diacetyl-p-toluidine or        1,3-diacylated hydantoins such as        1,3-diacetyl-5,5-dimethylhydantoin;    -   N-alkyl-N-sulfonylcarboxamides, e.g., N-methyl-N-mesylacetamide        or N-methyl-N-mesylbenzamide;    -   N-acylated cyclic hydrazides, acylated triazols or urazols,        e.g., monoacetylmaleic hydrazide;    -   O,N,N-trisubstituted hydroxylamines, e.g.,        O-benzoyl-N,N-succinylhydroxylamine,        O-acetyl-N,N-succinylhydroxylamine or        O,N,N-triacetylhydroxylamine;    -   N,N′-diacylsulfurylamides, e.g.,        N,N′-dimethyl-N,N′-diacetylsulfurylamide or        N,N′-diethyl-N,N′-dipropionylsulfurylamide;    -   triacyl cyanurates, e.g., triacetyl cyanurate or tribenzoyl        cyanurate;    -   carboxylic anhydrides, e.g., benzoic anhydride, m-chlorobenzoic        anhydride, or phthalic anhydride;    -   1,3-diacyl-4,5-diacyloxyimidazolines, e.g.,        1,3-diacetyl-4,5-diacetoxyimidazoline;    -   tetraacetylglycoluril and tetrapropionylglycoluril;    -   diacylated 2,5-diketopiperazines, e.g.,        1,4-diacetyl-2,5-diketopiperazine;    -   acylation products of propylene diurea and 2,2-dimethylpropylene        diurea, e.g., tetraacetylpropylene diurea;    -   α-acyloxypolyacylmalonamides, e.g.,        α-acetoxy-N,N′-diacetylmalonamide;    -   diacyldioxohexahydro-1,3,5-triazines, e.g.,        1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;    -   ammonium nitriles, e.g., N-methylmorpholinioacetonitrile        hydrogensulfate or trimethylammonioacetonitrile hydrogensulfate;    -   benz(4H)1,3-oxazin-4-ones having alkyl radicals, for example        methyl, or aromatic radicals, for example phenyl, in position 2.

The laundry detergent of the present invention may optionally furthercomprise bleach catalysts. Useful bleach catalysts include for examplequaternized imines and sulfonimines, described for example in U.S. Pat.No. 5,360,569 and EP-A 0 453 003. Particularly efficacious bleachcatalysts are manganese complexes, described for example in WO-A94/21777. Such compounds, if used in laundry detergents, areincorporated at not more than 1.5% by weight, more particularly not morethan 0.5% by weight. Further suitable metal catalysts are mentioned inAngew. Chem. 2006, 118, 212-229, for example.

To improve the conductivity of the basic electrolyte, conducting saltscan be added during the process or method and most simply as aconstituent of the laundry detergent. Useful conducting salts includefor example quaternary, preferably bisquaternary ammonium salts.Particular preference is given to the conducting salts selected from thegroup consisting of bis-N,N′-(tri C₁-C₈-alkyl)-substituted tri-, tetra-,penta-, hexa, etc -methylenediammonium salts such ashexamethylenebis(dibutyl-ethylammonium) phosphate or hydroxide. Veryparticular preference is given to usinghexamethylenebis(dibutylethylammonium) phosphate or hydroxide asconducting salt. If desired, the electrolyte is additionally admixedwith certain additives, such as EDTA or triethanolamine, preferably byadmixture to the laundry detergent of the present invention, in orderthat the cathodic deposition of iron, which would have an adverse effecton the desired high hydrogen overvoltage of the cathode, may becontrolled. Borates such as disodium diborate or orthoboric acid can beadded as anode corrosion inhibitors.

Builders

Useful inorganic builders (A′) include, in particular, crystalline oramorphous aluminosilicates having ion-exchanging properties such as,more particularly, zeolites. Various types of zeolites are suitable,more particularly zeolites A, X, B, P, MAP and HS in their Na form or informs in which Na has been partially exchanged for other cations such asLi, K, Ca, Mg or ammonium. Useful zeolites are described for example inEP-A 0 038 591, EP-A 0 021 491, EP-A 0 087 035, U.S. Pat. No. 4,604,224,GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384 070 and WO-A 94/24251.

Useful crystalline silicates (A′) include for example disilicates orsheet-silicates, for example SKS-6 (from Hoechst). Silicates can be usedin the form of their alkali metal, alkaline earth metal or ammoniumsalts, preferably as sodium, lithium and magnesium silicates.

Amorphous silicates such as, for example, sodium metasilicate, which hasa polymeric structure, or Britesil® H20 (from Akzo) can likewise beused.

Suitable inorganic builder substances based on carbonate are carbonatesand bicarbonates. These can be used in the form of their alkali metal,alkaline earth metal or ammonium salts. Preference is given to usingsodium, lithium and magnesium carbonates or bicarbonates, moreparticular sodium carbonate and/or sodium bicarbonate.

Customary phosphates useful as inorganic builders are polyphosphatessuch as pentasodium triphosphate, for example.

The recited compounds (A′) can be used individually or mixed with eachother. Of particular interest for use as an inorganic builder componentis a mixture of aluminosilicates and carbonates, more particularly ofzeolites, especially zeolite A, and alkali metal carbonates, especiallysodium carbonate, in a weight ratio ranging from 98:2 to 20:80, moreparticularly ranging from 85:15 to 40:60. In addition to this mixture,other components (A′) can be additionally present.

In a preferred embodiment, the laundry detergent of the presentinvention comprises 0.1% to 20% by weight and more particularly 1% to12% by weight of organic cobuilders (B′) in the form of low molecularweight, oligomeric or polymeric carboxylic acids, more particularlypolycarboxylic acids, or phosphonic acids or salts thereof, moreparticularly sodium or potassium salts.

Suitable low molecular weight carboxylic acids or phosphonic acids for(B′) are for example:

C₄-C₂₀ di-, tri- and tetracarboxylic acids such as for example succinicacid, propanetricarboxylic acid, butanetetracarboxylic acid,cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acidshaving C₂-C_(ie) alkyl or alkenyl radicals;C₄-C₂₀ hydroxy carboxylic acids such as for example malic acid, tartaricacid, gluconic acid, glutaric acid, citric acid, lactobionic acid andsucrosemono-, -di- and -tricarboxylic acid;amino polycarboxylic acids such as for example nitrilotriacetic acid,β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediaceticacid, isoserinediacetic acid, methylglycinediacetic acid and alkylethylenediaminetriacetates;salts of phosphonic acids such as hydroxyethanediphosphonic acid, forexample.

Suitable oligomeric or polymeric carboxylic acids for (B′) are forexample:

oligomaleic acids as described for example in EP-A 451 508 and EP-A 396303;co- and terpolymers of unsaturated C₄-C₈ dicarboxylic acids comprisingunits derived from monoethylenically unsaturated monomersof group (i) in amounts of up to 95% by weight,of group (ii) in amounts of up to 60% by weight, andof group (iii) in amounts of up to 20% by weight.

Useful unsaturated C₄-C₈ dicarboxylic acids here include for examplemaleic acid, fumaric acid, itaconic acid and citraconic acid. Maleicacid is preferred.

Group (i) comprises monoethylenically unsaturated C₃-C₈ monocarboxylicacids such as for example acrylic acid, methacrylic acid, crotonic acidand vinylacetic acid. Preference among group (i) is given to usingacrylic acid and methacrylic acid.

Group (ii) comprises monoethylenically unsaturated C₂-C₂₂ olefins, vinylalkyl ethers having C₁-C₈ alkyl groups, styrene, vinyl esters of C₁-C₈carboxylic acids, (meth)acrylamide and vinylpyrrolidone. Preferenceamong group (ii) is given to using C₂-C₆ olefins, vinyl alkyl ethershaving C₁-C₄ alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) comprises (meth)acrylic esters of C₁-C₈ alcohols,(meth)acrylonitrile, (meth)acrylamides of C₁-C₈ amines, N-vinylformamideand vinylimidazole.

When the polymers of group (ii) comprise units derived from vinylesters, these units may also be in a state of partial or completehydrolysis to vinyl alcohol structural units. Suitable co- andterpolymers are known for example from U.S. Pat. No. 3,887,806 and alsoDE-A 43 13 909.

Dicarboxylic acid copolymers useful for (B′) are preferably:

copolymers of maleic acid and acrylic acid in a weight ratio rangingfrom 10:90 to 95:5 and more preferably those in a weight ratio rangingfrom 30:70 to 90:10 with molar masses of 100 000 to 150 000;

terpolymers of maleic acid, acrylic acid and a vinyl ester of a C₁-C₃carboxylic acid in a weight ratio of 10 (maleic acid):90 (acrylicacid+vinyl ester) to 95 (maleic acid):10 (acrylic acid+vinyl ester),wherein the weight ratio of acrylic acid to vinyl ester can range from30:70 to 70:30;copolymers of maleic acid with C₂-C₈ olefins in a molar ratio rangingfrom 40:60 to 80:20, in which case copolymers of maleic acid withethylene, propylene or isobutene in a molar ratio of 50:50 areparticularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weightcarbohydrates or hydrogenated carbohydrates, cf. U.S. Pat. No.5,227,446, DE-A 44 15 623 and DE-A 43 13 909, are likewise useful as(B′).

Useful unsaturated carboxylic acids here are for example maleic acid,fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylicacid, crotonic acid and vinylacetic acid, and also mixtures of acrylicacid and maleic acid, which are grafted onto the component to begrafted, in amounts of 40% to 95% by weight, based on the component tobe grafted.

By way of modification, an additional up to 30% by weight, based on thecomponent to be grafted, of further monoethylenically unsaturatedmonomers can be present in copolymerized form. Suitable modifyingmonomers are the abovementioned monomers of groups (ii) and (iii).

Useful grafting bases include degraded polysaccharides such as forexample acidic or enzymatically degraded starches, inulins or cellulose,protein hydrolyzates and reduced (hydrogenated or reductively aminated)degraded polysaccharides such as for example mannitol, sorbitol,aminosorbitol and N-alkylglucamine, and also polyalkylene glycols havingmolar masses of up to M_(w)=5000 such as for example polyethyleneglycols, ethylene oxide-propylene oxide or ethylene oxide-butylene oxideor ethylene oxide-propylene oxide-butylene oxide block copolymers andalkoxylated mono- or polyhydric C₁-C₂₂ alcohols, cf. U.S. Pat. No.5,756,456.

Preference among this group is given to using grafted degraded ordegraded reduced starches and grafted polyethylene oxides, in which case20% to 80% by weight of monomers, based on the graft component, are usedin the graft polymerization. Grafting preferably utilizes a mixture ofmaleic acid and acrylic acid in a weight ratio ranging from 90:10 to10:90.

Polyglyoxylic acids useful as (B′) are described for example in EP-B 001004, U.S. Pat. No. 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The endgroups of the polyglyoxylic acids can have different structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acids usefulas (B′) are known for example from EP-A 454 126, EP-B 511 037, WO-A94/01486 and EP-A 581 452.

Useful as (B′) are also in particular polyaspartic acids orcocondensates of aspartic acid with further amino acids, C₄-C₂₅ mono- ordicarboxylic acids and/or C₄-C₂₅ mono- or diamines. Particularpreference is given to using polyaspartic acids prepared inphosphorus-containing acids and modified with C₆-C₂₂ mono- ordicarboxylic acids and/or with C₆-C₂₂ mono- or diamines.

Condensation products useful as (B′) of citric acid with hydroxycarboxylic acids or polyhydroxy compounds are known for example fromWO-A 93/22362 and WO-A 92/16493. Such carboxyl-containing condensatestypically have molar masses of up to 10 000, preferably up to 5000.

Ethylenediaminedisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, amino polyalkylene phosphonates and polyglutamates arefurther useful as (B′).

Oxidized starches can be used as organic cobuilders in addition to (B′).

Surfactants

Useful anionic surfactants (C) include for example fatty alcoholsulfates of fatty alcohols having 8 to 22 and preferably 10 to 18 carbonatoms, for example C₉-C₁₁ alcohol sulfates, C₁₂-C₁₄ alcohol sulfates,cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate andtallow fatty alcohol sulfate.

Further useful anionic surfactants include alkanesulfonates such asC₈-C₂₄ and preferably C₁₀-C₁₈ alkanesulfonates and also soaps such asfor example the sodium and potassium salts of C₈-C₂₄ carboxylic acids.

Further suitable anionic surfactants are C₉-C₂₀ linearalkylbenzenesulfonates (LASs) and alkyltoluenesulfonates.

Useful anionic surfactants (C) further include C₈-C₂₄ olefinsulfonatesand -disulfonates, which can also constitute mixtures of alkene- andhydroxyalkanesulfonates or -disulfonates, alkyl ester sulfonates,sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acidglycerol ester sulfonates, alkylphenol polyglycol ether sulfates,paraffinsulfonates having about 20 to about 50 carbon atoms (based onparaffin or paraffin mixtures recovered from natural sources), alkylphosphates, acyl isethionates, acyl taurates, acyl methyltaurates,alkylsuccinic acids, alkenylsuccinic acids or their monoesters ormonoamides, alkylsulfosuccinic acids or their amides, mono- and diestersof sulfosuccinic acids, acyl sarcosinates, sulfated alkylpolyglucosides,alkylpolyglycol carboxylates and also hydroxyalkylsarcosinates.

Anionic surfactants are preferably included in the fiber- andtextile-treating agent in the form of salts. Suitable cations in thesesalts are alkali metal ions such as sodium, potassium and lithium andammonium salts such as for example hydroxyethylammonium,di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts.

The amount in which component (C) is present in the fiber- andtextile-treating agent of the present invention is preferably in therange from 3% to 30% by weight and more particularly in the range from5% to 20% by weight. When C₉-C₂₀ linear alkylbenzenesulfonates (LASs)are also used, these are typically used in an amount up to 25% byweight, especially up to 20% by weight. It is possible to use just oneclass of anionic surfactants alone, for example just fatty alcoholsulfates or just alkylbenzenesulfonates, but it is also possible to usemixtures of different classes, for example a mixture of fatty alcoholsulfates and alkylbenzenesulfonates. Within the individual classes ofanionic surfactants, it is also possible to use mixtures of differentspecies.

A further class of useful surfactants is that of nonionic surfactants D,more particularly alkylphenol alkoxylates such as alkylphenolethoxylates having C₆-C₁₄ alkyl chains and from 5 to 30 mol of alkyleneoxide units.

Another class of nonionic surfactants is that of alkylpolyglucosides orhydroxyalkyl-polyglucosides having 8 to 22 and preferably 10 to 18carbon atoms in the alkyl chain. These compounds comprise usually from 1to 20 and preferably from 1.1 to 5 glucoside units. Another class ofnonionic surfactants is that of N-alkylglucamides having C₆-C₂₂ alkylchains. Such compounds are obtained for example by acylation ofreductively aminated sugars with appropriate long-chain carboxylic acidderivatives.

Useful nonionic surfactants (D) further include block copolymers ofethylene oxide, propylene oxide and/or butylene oxide (Pluronic® andTetronic® brands from BASF), polyhydroxy or polyalkoxy fatty acidderivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxypolyhydroxy fatty acid amides, fatty acid amide ethoxylates, moreparticularly end group capped ones, and also fatty acid alkanolamidealkoxylates.

The amount in which component (D) is present in the fiber- andtextile-treating agent of the present invention is preferably in therange from 1% to 20% by weight and more particularly in the range from3% to 12% by weight. It is possible to use just one class of nonionicsurfactants alone, more particularly just alkoxylated C₈-C₂₂ alcohols,but it is also possible to use mixtures of different classes. Within theindividual classes of nonionic surfactants it is also possible to usemixtures of different species.

Since the balance between the recited surfactant varieties is ofsignificance for the efficacy of the fiber- and textile-treating agentsof the present invention, anionic surfactants (C) and nonionicsurfactants (D) are preferably in a weight ratio ranging from 95:5 to20:80 and more particularly ranging from 80:20 to 50:50. The surfactantconstituents of the surfactant mixture of the present invention mustalso be taken into account here.

It is further also possible for cationic surfactants (E) to be presentin the fiber- and textile-treating agents of the present invention.

Useful cationic surfactants include for example ammonio-containingsurface-active compounds such as for example, alkyldimethylammoniumhalides and compounds of the general formula

RR′R″R″′N⁺X⁻

where R to R″′ are each alkyl, aryl, alkylalkoxy, arylalkoxy,hydroxyalkyl(alkoxy), hydroxyaryl(alkoxy) and X is a suitable anion.

The fiber- and textile-treating agents of the present invention mayoptionally also comprise ampholytic surfactants (F), for examplealiphatic derivatives of secondary or tertiary amines which comprise ananionic group in one of the side chains, alkyldimethylamine oxides oralkyl- or alkoxymethylamine oxides.

Components (E) and (F) can be present in the fiber- and textile-treatingagent at up to 25%, preferably 3-15%.

Enzymes

In a further preferred embodiment, the fiber- and textile-treating agentof the present invention additionally comprises 0.05% to 4% by weight ofenzymes (J). Enzymes used in fiber- and textile-treating agents arepreferably proteases, amylases, lipases and cellulases. The enzymes arepreferably added in amounts of 0.1-1.5% by weight, more preferably 0.2%to 1.0% by weight, of the formulated enzyme. Examples of suitableproteases are Savinase and Esperase (from Novo Nordisk). Lipolase (fromNovo Nordisk) is an example of a suitable lipase. Celluzym (from NovoNordisk) is an example of a suitable cellulase. It is similarly possibleto use peroxidases to activate the bleach system. It is possible to useindividual enzymes or a combination of different enzymes. If desired,the textile-washing agent formulation of the present invention mayfurther comprise enzyme stabilizers, for example calcium propionate,sodium formate or boric acids or salts thereof, and/or antioxidants.

A fiber treated by the process or method of the present invention orcontacted with a laundry detergent of the present invention constitutesa further part of the subject matter of the present invention. Thefibers can be not only natural fibers but also synthetic fibers.Nonexhaustive examples of natural fibers are: cotton, wool, linen andviscose fibers; nonexhaustive examples of synthetic fibers are:polypropene, polyamide, polyester, nylon-6,6, nylon-6, Teflon®, Lycra®fibers.

The fibers are preferably in a woven, loop-drawingly knitted, spun,loop-formingly knitted, knotted, bobbin-laced state.

The present invention will now be more particularly elucidated byexamples which do not restrict the subject matter of the invention:

EXAMPLES Experimental Setup

1000 mL jacketed glass vessel equipped with mechanical stirrer (IKAstirring motor with glass stirrer and mobile PTFE stirring blade) andliquid circuit (Iwaki magnetic pump MD6-230GS01, 80-90 L/h) and anelectrolysis cell with boron-doped diamond electrodes (AdamantminiDiaCell, diamond on silicon, 12.5 cm² electrode area). The testfabrics were introduced into the jacketed vessel at the start.

To evaluate the results of the electrochemical bleach, referenceexperiments were carried out with a comparative system of hydrogenperoxide (H₂O₂) and tetraacetyl-ethylenediamine (TAED) withoutelectrolysis. The concentration ranges chosen correspond to those ofcommercially available laundry detergents, in which TAED is currentlywidely used. The reference system used is a mixture of H₂O₂ and TAED ina ratio of 4:1 (mmol/L).

The reference experiments involved solutions of H₂O₂ and TAED incompletely ion-free water being prepared and recirculated at 40° C.without electrolysis. After 30 minutes, the fabric samples were removed,thoroughly rinsed with completely ion-free water, dried in the absenceof light and measured for reflectance as a measure of soil removal.

The washing liquid of reference experiment R3 has the followingcomposition: 700 g of completely ion-free water, 10 g of NaHCO₃, 0.32 gof H₂O₂ solution (30% H₂O₂ in water), 0.16 g of TAED (4:1 mmol/L).

The washing liquid for the inventive experiments with activeelectrolysis typically has the following composition: 700 g ofcompletely ion-free water, 10 g of NaHCO₃, 0.16 g of TAED.

Soil removal was determined by subjecting the test fabric to areflectance measurement at 460 nm before and after washing. The soil orcolor removal was determined from the reflectance values R before andafter washing and also the reflectance value of a white reference cottonfabric as per the following formula in %:

${{Soil}\mspace{14mu} {{removal}\lbrack\%\rbrack}} = {\frac{{R\left( {{after}\mspace{14mu} {wash}} \right)} - {R\left( {{before}\mspace{14mu} {wash}} \right)}}{{R\left( {{white}\mspace{14mu} {cotton}} \right)} - {R\left( {{before}\mspace{14mu} {wash}} \right)}} \times 100}$

All washes were carried out 2×. The soil removal values recited in thetable under the wash results correspond to the average of measurementsobtained under identical conditions.

The reflectance measurements were carried out using a Gretag MacbethSpectrolino spectrophotometer under the following conditions: observerangle 10°, illuminant D65, UV filter.

Reference Example R 1 and Example 1

Reference example R 1 describes the soil removal brought about solely bythe washing solution (700 g of completely ion-free water, 10 g ofNaHCO₃). This experiment constitutes a reference for determining thesoil removal achieved.

Example 1 describes the bleaching effect achieved by electrolysis of thewashing solution (700 g of completely ion-free water, 10 g of NaHCO₃) atboron-doped diamond electrodes without the addition of a bleachactivator or bleach precursor such as TAED for example. Compared withreference test R 1, a significant increase in soil removal is observed.

TABLE 1 Soil removal exemplified for EMPA 167 test fabric (tea oncotton). Soil removal in % at 40° C. (reflectance measurement at 460 nm)Example Electrolysis time 30 min R1 —^(a) 12 1 30 min^(b) 26 ^(a)700 gof completely ion-free water, 10 g of NaHCO₃ ^(b)30 min electrolysis at1.2 A (700 g of completely ion-free water, 10 g of NaHCO₃).

Examples 2 to 6

Examples 2 to 6 demonstrate the soil removal (EMPA 167 test fabric, teaon cotton) achieved as a function of the current strength using theinventive process/method in the presence of TAED bleach activator.

TABLE 2 Influence of current strength on soil removal (tea on cotton,EMPA 167). Soil removal in % at 40° C.^(a) (reflectance measurement at460 nm) Example Current strength Electrolysis time 30 min 2 0.06 A  29 30.12 A  47 4 0.6 A 49 5 1.2 A 59 6 6.0 A 67 ^(a)The electrolyte used(washing liquid) typically has the following composition: 700 g ofcompletely ion-free water, 10 g of NaHCO₃, 0.16 g of TAED

The results reflect the influence of the current strength on soilremoval. It was found that the soil removal achieved increases withincreasing current strength.

Reference Examples R 2 to R 4

Reference examples R 2 to R 4 represent the results of bleaching with asystem of H₂O₂ and TAED in differing composition. The washing solutionwith an addition of H₂O₂/TAED in a concentration ratio of 4:1 (mmol/1)thus corresponds to a composition frequently used in commerciallyavailable washing powders.

TABLE 3 Influence of composition of H₂O₂/TAED on soil removal asexemplified for EMPA 167 test fabric (tea on cotton). Soil removal in %at 40° C. (reflectance measurement at 460 nm) Example H₂O₂/TAED [mmol/L]Run time 30 min R2 8/1 72 R3 4/1 64 R4   4/0.5 59

It was found, as expected, that increasing the H₂O₂ concentration to 8/1(R 2) results in greater soil removal, since the formation of peraceticacid from TAED is favored. It was similarly found that the degree ofsoil removal likewise depends on the available amount of TAED. Halvingthe TAED concentration from 4/1 (R 3) to 4/0.5 (R 4) thus leads to adecrease in soil removal from 64% to 59%.

Comparing soil removal due to electrochemical bleach activation with theresults of the reference tests shows that the electrochemical processachieves a degree of soil removal comparable to that of the H₂O₂/TAED4:1 (mmol/1) system (about 60% soil removal after 30 minutes at 40° C.,see Example 5).

Examples 7 and 8

Examples 7 and 8 describe the difference between sequential splitting ofthe two steps (Example 7) and parallelization of electrolysis andcleaning operation (Example 8) on the soil removal result.

TABLE 4 Influence of electrolysis time on soil removal (EMPA 167 testfabric) Soil removal in % at 40° C. Pre-electrolysis [min]/ (reflectancemeasurement at 460 nm) Example electrolysis [min] 30 min after TAEDaddition 7 10/0  46 8 10/30 61

The standard procedure was to move the washing solution past theelectrodes at 1.2 A throughout the entire reaction time, and very goodsoil removal was achieved (Example 5). Surprisingly, very good soilremoval was likewise achieved when the washing solution was recirculatedat 1.2 A for 10 minutes before addition of TAED and test fabric. Afterthe current source was switched off, TAED and test fabric were added,followed by recirculation for 30 minutes without further application ofelectric current (Example 7). This effect is very advantageous sincevery good soil removal can be achieved with a lower input of current.Soil removal can be increased to 61% when the washing solution isrecirculated at 1.2 A for 10 minutes before addition of TAED and testfabric and the electrolysis is continued for 30 minutes after theaddition of TAED and test fabric (Example 8).

Examples 9 to 12 and Reference Examples R 5 and R 6

Examples 9 to 12 and also Reference Examples R 5 and R 6 describe thetreatment of various stain types with the inventive process forelectrochemical bleach activation. The results show that the soilremoval achieved varies, as expected, with regard to different stains.Comparative examples R 5 and R 6 each describe the pure washing effectin the absence of TAED and without electrolysis. They show that theprocess of the present invention gives good soil removal not only withregard to red wine (Examples 9 and 10) but also with regard to blueberryjuice (Examples 11 and 12).

TABLE 5 Soil removal exemplified for EMPA 114 test fabric (red wine oncotton). Soil removal in % at 40° C. (reflectance measurement at 460 nm)Run time from addition of TAED and/or Example Current strength [A] testcloth: 30 min  9 1.2^(a) 55 10 1.2^(b) 64 R5 —^(c) 39 ^(a)30 minelectrolysis at 1.2 A without addition of TAED. ^(b)10 minpre-electrolysis at 1.2 A, then addition of TAED (1 mmol/L based ontotal volume of washing solution), 30 min recirculation without furtherelectrolysis at 40° C. ^(c)30 min recirculation at 40° C. withoutelectrolysis (700 g of completely ion-free water, 10 g of NaHCO₃)

TABLE 6 Soil removal exemplified for WFK 10WB test fabric (blueberry oncotton). Soil removal in % at 40° C. (reflectance measurement at 460 nm)Run time from addition of TAED Example Current strength [A] and/or testcloth: 30 min 11 1.2^(a) 84 12 1.2^(b) 83 R6 —^(c) 53 ^(a)30 minelectrolysis at 1.2 A without addition of TAED. ^(b)10 minpre-electrolysis at 1.2 A, then addition of TAED (1 mmol/L based ontotal volume of washing solution), 30 min recirculation without furtherelectrolysis at 40° C. ^(c)30 min recirculation at 40° C. withoutelectrolysis (700 g of completely ion-free water, 10 g of NaHCO₃)

Examples 13 to 26 and Reference Examples R 7 to R 20

Examples 13-26 and also Reference Examples R 7-R 20 describe thetreatment of various textile colors with the inventive process forelectrochemical bleach activation. To this end, a solution of 15.4 g ofsodium bicarbonate in 1084 g of completely ion-free water waselectrolyzed at 40° C. and 1.2 A for 10 minutes. Next 0.25 g of TAED andthe color monitors were added, before electroless recirculation for 45minutes. After every washing operation, the color monitors were brieflyrinsed off with completely ion-free water and after every 5 wash cyclessubjected to a reflectance measurement at 460 nm to determine the degreeof color removal. Altogether, 15 wash cycles (3×5) were carried out percolor monitor. As Table 7 shows, the inventive process surprisingly doesnot give rise to any significant color damage within the error ofmeasurement. One exception is the fabric dyed with Sulphur Black 1(AISE-1) (Example 13), which tends to lose color/bleed even in a washliquor without bleach and without electrolysis.

TABLE 7 Investigations concerning color damage by the inventive processusing selected color monitors after 15 wash cycles. Color removal in % 5wash 10 wash 15 wash Example Color monitor cycles cycles cycles 13AISE-1 3% 7% 13% 14 AISE-3 −3% −3% −3% 15 AISE-5 −4% −5% −5% 16 AISE-8−1% −1% −1% 17 AISE-16 −1% −1% −1% 18 AISE-20 1% 1% 3% 19 AISE-21 0% 0%1% 20 AISE-22 1% 2% 3% 21 AISE-24 −22% −20% −17% 22 AISE-26 3% 3% 5% 23AISE-27 −1% 0% 0% 24 AISE-29 0% 0% 0% 25 AISE-33 0% 0% 0% 26 AISE-39 0%0% 0%

The results of the inventive process were compared with a simplifiedreference system. To investigate color removal from selected textilecolors, the color monitors were stirred in a system of 15.4 g of sodiumbicarbonate, 1085 g of completely ion-free water, 0.25 g of TAED and0.44 g of hydrogen peroxide solution (30% of H₂O₂ in water) at 40° C.for 45 minutes. The results of the reference tests are summarized inTable 8. Again, as mentioned above, a very pronounced change isnoticeable (R 7) for the color monitor dyed with Sulphur Black 1(AISE-1). Comparison of the other data shows that the reference systemgenerally leads to greater color damage than the inventive process.

TABLE 8 Investigations concerning color damage by a reference systemusing selected color monitors after 15 wash cycles. Color removal in % 5wash 10 wash 15 wash Example Color monitor cycles cycles cycles R7AISE-1 9% 21% 32% R8 AISE-3 −4% −4% −4% R9 AISE-5 −4% −5% −6% R10 AISE-8−1% −1% −1% R11 AISE-16 −1% −1% −1% R12 AISE-20 3% 5% 8% R13 AISE-21 1%2% 3% R14 AISE-22 3% 7% 11% R15 AISE-24 −26% −23% −22% R16 AISE-26 4% 6%8% R17 AISE-27 −1% 0% 0% R18 AISE-29 0% 1% 1% R19 AISE-33 0% 0% 0% R20AISE-39 0% 0% 0%

1. A washing machine comprising an electrode and a closed-loop controlunit, wherein a current strength in the range from 0.02 to 30 A can beapplied to the electrode during the washing operation.
 2. The washingmachine according to claim 1 wherein the electrode is selected from thegroup consisting of lead electrode, diamond electrode, stainless-steelelectrode, platinum electrode and tin oxide electrode.
 3. The washingmachine according to claim 2 wherein the electrode is a diamondelectrode.
 4. The washing machine according to any preceding claimwherein the electrode has an effective surface area in the range from0.5 to 1000 cm².
 5. A process for cleaning fibers, which comprisesgenerating free OH radicals and/or H₂O₂ in aqueous solution by applyinga current strength in the range from 0.02 to 30 A to an electrode. 6.The process according to claim 5 wherein the electrode is a diamondelectrode having an effective surface area in the range from 0.5 to 1000cm².
 7. The process according to claim 5 or 6 wherein at least onecompound selected from the group consisting of builder, surfactant andenzyme is used for cleaning as well as the free OH radicals (ordescendent products).
 8. The process according to any one of claims 5 to7 carried out at a temperature of up to 60° C.
 9. The process accordingto any one of claims 5 to 8 having an at least 20% degree of soilremoval for bleachable stains.
 10. A laundry detergent comprising bleachactivator(s) and/or bleach catalyst(s) and less than 1% by mass ofhydrogen peroxide or of hydrogen peroxide releaser compounds.
 11. Alaundry detergent, selected from the group consisting of fully builtlaundry detergent, liquid laundry detergent, color detergent and wooldetergent.
 12. A method of using a washing machine according to any ofclaims 1 to 4 and a laundry detergent according to claim 10 or
 11. 13. Afiber treated by a process or method according to claim 5 to 9 or 12 orcontacted with a laundry detergent according to claim 10 or
 11. 14. Akit of parts, comprising a washing machine and an electrolytic cellconnectable upstream of the water inlet.
 15. An e-bleach ball comprisinga power supply independent of the electricity grid, a diamond anode anda cathode, which are arranged such that the electrodes are able to comeinto contact with the electrolyte when the e-bleach ball is in thewashing drum of a washing machine during the washing operation.